CN108137857B - Polycarbonate compositions with improved stabilization - Google Patents

Abstract

The present invention relates to a composition comprising A) at least one polymer selected from aromatic polycarbonates and aromatic polyester carbonates, and B) at least one polymer selected from compounds of general formulae (I) and (II) Bronsted acid compounds (R1) _y1 ‑N‑[R2‑COOH] _x1 (I)[HOOC‑R2] _x2 (R1) _y2 N‑(R3)‑N(R1) _y3 [R2‑COOH] _x3 (II) wherein R1 represents optionally functionalized or heteroatom-substituted alkyl, aryl or cycloalkyl, R2 represents C1- to _C8 -alkylene or _C2- to _{C8 -} alkylidene, R3 represents –(CH ₂ ) _n –, –(CH ₂ ) _n [O(CH ₂ ) _n ] _m – or –(CH ₂ ) _n [NR4(CH ₂ ) _n ] _m –, where n is an integer and m is an integer, R4 represents an optionally functionalized or heteroatom-substituted alkyl, aryl or cycloalkyl group, x1 is an integer from 1 to 3, x2 and x3 are 1 or 2, respectively, and y1 is determined by the formula y1=3–x1 Calculated, y2 is calculated by the formula y2=2–x2, y3 is calculated by the formula y3=2–x3, and wherein in compounds with a plurality of groups R1 and/or R2, these groups can independently represent different or the same The group having the above-mentioned definition, also relates to a method for preparing a composition using components A, B and optionally other components, wherein at least one of the components used plays a basic role or contains a component that plays a basic role, involving The composition obtained by this method and the use of the composition for the manufacture of mouldings and the mouldings themselves.

Description

Polycarbonate compositions with improved stabilization

The present invention relates to thermoplastic polycarbonate compositions containing Bronsted acidic compounds, to a process for preparing thermoplastic polycarbonate compositions, to the use of the compositions for producing moldings, and to the moldings themselves.

In the preparation of polycarbonate compositions, it is said that components which act as alkalinizing agents or components which contain components which act as alkalinizing agents are frequently used, since the achievement of specific desired technical properties or functions or the further work-up (purification) of these components is thereby disadvantageous, impossible or undesirable for process engineering reasons.

Basic components which may be contained in the components for the preparation of the impact-modified polycarbonate compositions are, for example, impurities resulting from the manufacture and/or additives which are deliberately added to these components.

Thus, for example, many commercially available fillers, such as talc or other commercially available polymer additives, for example several antistatics (e.g. polyetheramides), lubricants and mold release agents (e.g. ethylenebisstearamide), stabilizers (e.g. benzotriazoles or sterically hindered amines used as light stabilizers), pigments (e.g. titanium dioxide), nitrogen-containing organic dyes (e.g. azo compounds or pyrazolones) and nitrogen-containing flame retardants (e.g. phosphoric acid amides)) exhibit basic behavior or contain ingredients which act in a basic manner. In addition, impact modifiers used in the preparation/compounding of polycarbonate compositions often contain ingredients that are basic in nature as a result of manufacture. This also includes residual amounts of substances which have an alkaline action, which are used as polymerization assistants, for example as emulsifiers in the emulsion polymerization or in the work-up, for example as assistants in the precipitation. The polycarbonates themselves may also contain residual amounts of basic components resulting from the manufacture, for example traces of sodium hydroxide from the washing and/or basic polymerization catalysts.

These basic components or constituents may catalytically decompose polycarbonate at elevated temperatures, such as those temperatures which are frequently encountered in the preparation and processing of polycarbonate molding compositions. Such polycarbonate degradation is often manifested as a loss of properties or a change in the surface of the molding compound. The choice of possible raw materials for such polycarbonate compositions is therefore very severely limited.

It is known from the prior art to add acidity to polycarbonate compositions in order to neutralize the harmful effects of alkaline components or ingredients which act alkaline.

WO 85/02622 a1 discloses color-stable polycarbonate-polyester compositions comprising an aromatic polycarbonate, a polyester and 0.01 to 1.00% by weight of a phosphorus-acidic (phorsauren) compound selected from the group consisting of phosphorous acid, phenylphosphonic acid and phosphorous acid derivatives substituted with fluorinated hydrocarbyl groups.

JP 02-018332B discloses polycarbonate resins stabilized with 2 to 20 ppm phosphorous acid and 50 to 300 ppm tris (2, 6-di-tert-butylphenyl) phosphite having good mechanical properties, hot water resistance and reduced yellowing under thermal stress.

US 2006/0287422 a1 describes thermoplastic compositions containing polycarbonate, mineral filler and an acid or acid salt and optionally further thermoplastic polymers as blend partners, for example selected from polyesters and (rubber-modified) vinyl (co) polymers. This application discloses that by adding an acid or an acidic salt, the heat-induced reduction in the molecular weight of the polycarbonate is reduced and thus the impact strength and ductility are improved.

EP 0576950A 2 and WO 2007/065579A 1 describe polycarbonate-ABS compositions which contain basic components and are stabilized with organic carboxylic acids.

WO 2010/063381A 1 describes impact-modified polycarbonate compositions having the improved combination of hydrolysis and processing stability, containing polycarbonate, an alkali-contaminated emulsion graft polymer and an acidic phosphorus compound having at least one P-OH functionality.

WO 2009/118114 a1 discloses polycarbonate compositions with a combination of improved light natural color (Rohton) and good hydrolysis-and processing stability containing polycarbonate, a rubber-modified graft polymer which contains residues of fatty acid salt emulsifiers as a result of manufacture, wherein the graft polymer in aqueous dispersion has a pH of more than 7, and an acidic additive. Hydroxy-functionalized mono-and polycarboxylic acids and phosphoric acid and the sodium-/potassium salts of phosphoric acid are disclosed in this application as acidic additives.

WO 2013/060687 a1 discloses polycarbonate compositions with good natural hue, improved thermal stability and improved processing stability (which is measured by the stability of the gloss with changing processing temperature) containing bronsted acidic compounds applied to inorganic or organic absorbents. Phosphoric acid, phosphorous acid, phosphinic acid and alkylated or arylated derivatives thereof are disclosed as examples of Bronsted acidic compounds.

WO 2013/060685 a1 discloses a process for preparing stabilized impact-modified polycarbonate compositions, in which an acidic compound in a highly dilute aqueous solution is applied to a graft polymer powder, and this powder, thus wetted with an aqueous solution of an acid, is then compounded.

However, the addition of the acids described in the prior art often leads to disadvantageous properties in polycarbonate compositions, such as a severe molecular weight reduction or the occurrence of surface defects under hot and humid storage conditions, a deterioration of the natural hue and/or a severe change in the surface gloss at high processing temperatures, or a stable preparation process can only be achieved within a very limited thermal processing window.

It is therefore desirable to provide polycarbonate compositions which, even when using one or more basic-acting raw material components or raw material components containing basic-acting ingredients, are distinguished by an improved combination of light intrinsic hue, high gloss, good processing stability, measured by a reduction in the molecular weight of the polycarbonate under thermal stress during shaping and a change in the intrinsic color (yellowing) and in the gloss (reduction), and improved hydrolytic stability, measured by a reduction in the molecular weight of the polycarbonate in humid climates with high relative air humidity, and are suitable for producing moldings whose surfaces have high gloss and few surface defects also after storage under humid and hot conditions.

It would also be desirable to provide polycarbonate compositions that exhibit advantageous properties even when at least one of the raw material components used to prepare the composition is a polymer that, as a result of manufacture, contains an alkali metal-, alkaline earth metal-, aluminum-or transition metal salt of a strong inorganic acid, such as a chloride, sulfate or nitrate.

It has now been found that, surprisingly, compositions containing the following components have advantageous properties

A) At least one polymer selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates, and

B) at least one Bronsted acidic compound selected from the group consisting of compounds of the general formulae (I) and (II)

(R1)_y1-N-[R2-COOH]_x1(I)

[HOOC-R2]_x2(R1)_y2N-(R3)-N(R1)_y3[R2-COOH]_x3(II)

Wherein

R1 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

r2 represents C₁-to C₈Alkylene or C₂-to C₈Alkylidene, preferably C₁-to C₄Alkylene or C₂-to C₄Alkylidene, more preferably C₁-to C₂Alkylene or C₂-to C₃An alkylidene group, very particularly preferably a methylene group,

r3 represents- (CH)₂)_n–、–(CH₂)_n[O(CH₂)_n]_m-or- (CH)₂)_n[NR4(CH₂)_n]_m–，

n is an integer, preferably 1 or 2, particularly preferably 2,

m is an integer, preferably 1 or 2,

r4 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by a heteroatom, preferably-CH₂COOH，

x1 is an integer from 1 to 3, preferably 3,

x2 and x3 are each 1 or 2, preferably 2

And is

y1 is calculated by the formula y1= 3-x 1,

y2 is calculated by the formula y2= 2-x 2,

y3 is calculated by the formula y3= 2-x 3,

and wherein in the compounds having a plurality of radicals R1 and/or R2, these radicals may, independently of one another, represent different or identical radicals having the abovementioned definition.

The compositions according to the invention preferably contain from 0.00001 to 0.5% by weight of component B.

In one embodiment, the composition is made using one or more alkaline acting components or components containing alkaline acting ingredients.

In a preferred embodiment, the composition contains not only components A and B, but also one or more rubber-containing graft polymers and/or rubber-free vinyl (co) polymers as component C.

In another preferred embodiment, the composition contains not only a and B but also additives as component D.

In another preferred embodiment, the composition contains components A, B, C and D.

In another embodiment, the composition contains not only A, B, optionally C and optionally D, but also one or more polyesters as component E. In these compositions, it is preferred to use only rubber-containing graft polymers as component C.

In a preferred embodiment, the composition consists of components A, B, C and D.

In another embodiment, the composition contains a polymer containing an alkali metal-, alkaline earth metal-, aluminum-, or transition metal salt of a strong mineral acid, such as a chloride, sulfate, or nitrate.

In a particular embodiment, the composition contains a polymer containing an alkaline earth metal salt of a strong mineral acid, such as magnesium sulfate and/or calcium chloride.

In another particular embodiment, the salt is contained in component C.

In a preferred embodiment, component B is used in the minimum amount necessary to achieve the desired processing stability. This amount depends on the type and amount of the alkaline-acting component and/or the component containing the alkaline-acting component used in the respective composition and therefore cannot generally be estimated, but must be determined for the respective composition by a series of experiments with different amounts of component B.

There is also a need to provide a thermal process for the preparation of thermoplastic polycarbonate compositions having the above properties which is stable within a broadened process window, i.e. at elevated melting temperatures and/or extended residence times, even using one or more basic-acting or basic-acting ingredient-containing raw components.

The present invention therefore further provides a process comprising steps (i), (ii) and optionally (iii), characterised in that

In the first step (i)

Heating the above-mentioned components A) and B) and optionally further components by supplying heat and/or mechanical energy, thereby melting at least component A, said components being dispersed in each other, followed by degassing the resulting composition in the form of a melt, optionally by applying an underpressure,

and in a further step (ii)

Re-solidifying the resulting composition by cooling

And granulated in a further step (iii),

wherein these further steps (ii) and (iii) may be performed in any order.

That is, in a process using both step (ii) and (iii), the melt may be first cooled and thus solidified and subsequently granulated, or alternatively, the melt may be cut and thereafter solidified by cooling.

An example of the former embodiment is strand granulation (strangularation), and an example of the alternative embodiment is underwater granulation.

In one embodiment, one or more components which function as bases or components containing components which function as bases are used in the process.

The process according to the invention is carried out using a melt compounding device. Preferred apparatuses are single-screw extruders, internal kneaders, co-kneaders, planetary screw extruders, ring extruders and twin-screw or multi-screw extruders, with or without kneading pins (Knetstiften). The twin-screw or multi-screw extruders used can be co-rotating or counter-rotating and are closely meshed or tangential.

Particularly preferred are co-kneaders, co-rotating twin-screw or multi-screw extruders and ring extruders.

Particularly preferred are co-rotating, closely intermeshing twin screw extruders.

As regards the components used in the process of the invention, the same preferred ranges as described above for the composition of the invention apply.

In a preferred embodiment, the composition of the invention in the process of the invention is made from the following components:

10 to 99.995 parts by weight, more preferably 30 to 95 parts by weight, particularly preferably 40 to 90 parts by weight, very particularly preferably 50 to 80 parts by weight of component A,

from 0.00001 to 0.5 part by weight, more preferably from 0.0001 to 0.3 part by weight, particularly preferably from 0.001 to 0.2 part by weight, very particularly preferably from 0.01 to 0.1 part by weight, of component B,

from 0 to 90 parts by weight, more preferably from 0 to 70 parts by weight, particularly preferably from 1 to 60 parts by weight, very particularly preferably from 10 to 50 parts by weight, of component C,

from 0 to 50 parts by weight, more preferably from 0.1 to 40 parts by weight, particularly preferably from 0.2 to 30 parts by weight, very particularly preferably from 0.5 to 25 parts by weight, of component D,

wherein the sum of the parts by weight of components A to D is standardized to 100.

In a further embodiment, the composition of the invention in the method of the invention is made from the following components:

10 to 99.995 parts by weight, more preferably 30 to 95 parts by weight, particularly preferably 40 to 90 parts by weight, very particularly preferably 50 to 80 parts by weight of component A,

from 0.00001 to 0.5 part by weight, more preferably from 0.0001 to 0.3 part by weight, particularly preferably from 0.001 to 0.2 part by weight, very particularly preferably from 0.01 to 0.1 part by weight, of component B,

from 0 to 50 parts by weight, more preferably from 0 to 40 parts by weight, particularly preferably from 1 to 30 parts by weight, very particularly preferably from 5 to 20 parts by weight, of component C,

from 0 to 50 parts by weight, more preferably from 0.1 to 40 parts by weight, particularly preferably from 0.2 to 30 parts by weight, very particularly preferably from 0.5 to 25 parts by weight, of component D,

from 1 to 90 parts by weight, more preferably from 10 to 70 parts by weight, particularly preferably from 15 to 60 parts by weight, very particularly preferably from 20 to 50 parts by weight, of component E,

wherein, in the case of the use of component E, component C is selected from one or more graft polymers having a gel content of in each case at least 75% by weight, based on component C,

and wherein the sum of the parts by weight of components A to E is standardized to 100.

Another embodiment of the present invention is a method for improving the combination of light intrinsic color, high gloss, good processing stability and hydrolytic stability of polycarbonate compositions, wherein one or more basic-acting or alkaline-acting-containing starting components and at least one acid according to component B are used, and wherein the required amount of acid is determined experimentally, preferably by using a series of experiments with different acid concentrations.

Another embodiment of the present invention is the use of Bronsted acidic compounds according to formula (I) or (II) for stabilizing polycarbonate compositions which are optionally prepared from one or more basic starting components or starting components containing basic components.

Another embodiment of the present invention is the use of Bronsted acidic compounds according to formula (I) or (II) for improving the combination of light intrinsic color, high gloss, good processing stability and hydrolytic stability of polycarbonate compositions which are optionally prepared from one or more basic-acting or alkaline-acting-containing starting components.

Component A

Aromatic Polycarbonates and/or aromatic polyester carbonates of component A which are suitable according to the invention are known in the literature or can be produced by processes known in the literature (for the production of aromatic Polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and DE-AS 1495626, DE-A2232877, DE-A2703376, DE-A2714544, DE-A3000610, DE-A3832396; for the production of aromatic polyester carbonates, for example DE-A3077934).

Aromatic polycarbonates are produced, for example, by reacting diphenols with carbonyl halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or greater than trifunctional branching agents, for example triphenols or tetraphenols. They can likewise be produced by the melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate.

Diphenols for the production of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (I)

Wherein

A is a single bond, C₁To C₅Alkylene radical, C₂To C₅Alkylidene, C₅To C₆-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO₂C which may be condensed with other aromatic rings optionally containing hetero atoms₆To C₁₂An arylene group,

Or a group of the formula (II) or (III)

B is in each case C₁To C₁₂Alkyl, preferably methyl, halogen, preferably chlorine and/or bromine,

x is in each case independently 0, 1 or 2,

p is 1 or 0, and

R⁵and R⁶Can be directed to each X¹Independently selected from each other and independently of each other hydrogen or C₁To C₆-an alkyl group, preferably hydrogen, methyl or ethyl,

x1 is carbon and

m is an integer of 4 to 7, preferably 4 or 5, with the proviso thatAt least one atom X¹Upper R⁵And R⁶And is an alkyl group.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C₁-C₅-alkane, bis (hydroxyphenyl) -C₅-C₆Cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and α -bis (hydroxyphenyl) diisopropylbenzene and also their ring-brominated and/or ring-chlorinated derivatives.

Particularly preferred diphenols are 4,4' -dihydroxydiphenyl, bisphenol A, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl sulfone as well as di-and tetrabrominated or chlorinated derivatives of these, such as, for example, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane or 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane. 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferred.

The diphenols may be used individually or in the form of any mixtures. The diphenols are known from the literature or are obtainable by processes known from the literature.

Examples of chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol or 2,4, 6-tribromophenol, and also long-chain alkylphenols, such as 4- [2- (2,4, 4-trimethylpentyl) ] phenol, 4- (1, 3-tetramethylbutyl) phenol according to DE-A2842005 or monoalkylphenols or dialkylphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, such as 3, 5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3, 5-dimethylheptyl) phenol and 4- (3, 5-dimethylheptyl) phenol. The amount of chain terminators to be used is generally from 0.5 mol% to 10 mol% of the molar sum of the diphenols used in each case.

The thermoplastic aromatic polycarbonates may be branched in a known manner and preferably by incorporation of 0.05 to 2.0 mol%, based on the total amount of diphenols used, of trifunctional or greater than trifunctional compounds, for example compounds having 3 or more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates according to the invention according to component A, 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of diphenols used, of polydiorganosiloxanes with hydroxyaryloxy terminal groups may also be used. These are known (US 3419634) and can be manufactured by methods known in the literature. The production of polydiorganosiloxane-containing copolycarbonates is described in DE-A3334782.

Preferred polycarbonates are not only bisphenol A homopolycarbonates but also copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of other diphenols, in particular of 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, which are mentioned as preferred or particularly preferred.

Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4, 4' -dicarboxylic acid and naphthalene-2, 6-dicarboxylic acid.

Particularly preferred are mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20: 1.

In the production of polyester carbonates, carbonyl halides, preferably phosgene, are additionally used together as bifunctional acid derivatives.

Chain terminators which are considered for the production of the aromatic polyester carbonates are not only the monophenols mentioned above but also their chlorocarbonates and optionally C₁To C₂₂Acid chlorides of alkyl or aromatic monocarboxylic acids substituted by halogen atoms and aliphatic C₂To C₂₂Monocarboxylic acid chlorides.

The amount of chain terminators is in each case 0.1 to 10 mol%, based in the case of phenolic chain terminators on moles of diphenols and in the case of monocarboxylic acid chloride chain terminators on moles of dicarboxylic acid dichlorides.

The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates may be both linear and branched in a known manner (see DE-A2940024 and DE-A3007934 in this connection).

Branching agents which may be used are, for example, trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3',4,4' -benzophenone tetracarboxylic acid tetrachloro, 1,4,5, 8-naphthalenetetracarboxylic acid tetrachloro or pyromellitic acid tetrachloro, in amounts of from 0.01 to 1.0 mol%, based on the diphenols used, or trifunctional or polyfunctional phenols, such as phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -hept-2-ene, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 1,1, 1-tris (4-hydroxyphenyl) ethane, in amounts of from 0.01 to 1.0 mol%, based on the dicarboxylic acid dichlorides used, Tris- (4-hydroxyphenyl) phenylmethane, 2-bis [4, 4-bis (4-hydroxyphenyl) cyclohexyl ] propane, 2, 4-bis (4-hydroxyphenylisopropyl) phenol, tetrakis- (4-hydroxyphenyl) methane, 2, 6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) propane, tetrakis- (4- [ 4-hydroxyphenylisopropyl ] phenoxy) methane, 1, 4-bis [4,4' -dihydroxytriphenyl ] methyl ] benzene. Phenolic branching agents may be initially charged with the diphenols, acid chloride branching agents may be introduced together with the acid dichlorides.

The content of carbonate structural units in the thermoplastic, aromatic polyester carbonates can be varied at will. The content of carbonate groups is preferably at most 100 mol%, in particular at most 80 mol%, particularly preferably at most 50 mol%, of the sum of ester groups and carbonate groups. Both the ester component and the carbonate component of the aromatic polyester carbonates may be present in the polycondensate in the form of blocks or in a randomly distributed manner.

In a preferred embodiment, component A has a weight-average molecular weight Mw (determined by Gel Permeation Chromatography (GPC) using polycarbonate standards in methylene chloride) of from 15000 g/mol to 50000 g/mol, preferably from 22000 g/mol to 35000 g/mol, in particular from 24000 to 32000 g/mol.

As component A it is possible to use polycarbonates or polyester carbonates or mixtures of polycarbonates and/or polyester carbonates according to the description above.

Component B

Component B is a Bronsted acidic compound selected from compounds of the general formulae (I) and (II)

(R1)_y1-N-[R2-COOH]_x1(I)

[HOOC-R2]_x2(R1)_y2N-(R3)-N(R1)_y3[R2-COOH]_x3(II)

Wherein

R1 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

r2 represents C₁-to C₈Alkylene or C₂-to C₈Alkylidene, preferably C₁-to C₄Alkylene or C₂-to C₄Alkylidene, more preferably C₁-to C₂Alkylene or C₂-to C₃An alkylidene group, very particularly preferably a methylene group,

r3 represents- (CH)₂)_n–、–(CH₂)_n[O(CH₂)_n]_m-or- (CH)₂)_n[NR4(CH₂)_n]_m–，

n is an integer, preferably 1 or 2, particularly preferably 2,

m is an integer, preferably 1 or 2,

r4 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by a heteroatom, preferably-CH₂COOH，

x1 is an integer from 1 to 3, preferably 3,

x2 and x3 are each 1 or 2, preferably 2

And is

y1 is calculated by the formula y1= 3-x 1,

y2 is calculated by the formula y2= 2-x 2,

y3 is calculated by the formula y3= 2-x 3,

and wherein in the compounds having a plurality of radicals R1 and/or R2, these radicals may, independently of one another, represent different or identical radicals having the abovementioned definition.

Component B is preferably selected from the following compounds:

ethylenediaminetetraacetic acid (EDTA) nitriloacetic acid

Ethylene glycol bis (aminoethyl ether) -N, N, N ', N' -tetraacetic acid (EGTA)

Diethylene Triamine Pentaacetic Acid (DTPA)

Component B is particularly preferably ethylenediaminetetraacetic acid (EDTA).

Component C

Component C is C1, C2 or C3 or a mixture of a plurality of these components.

Component C1

Component C1 is a graft polymer prepared by grafting C1.1) onto C1.2) in an emulsion polymerization process

C1.1) from 5 to 95% by weight, preferably from 10 to 70% by weight, particularly preferably from 20 to 60% by weight, based on the component C1, of a mixture of C1.1.1) and C1.1.2)

C1.1.1) from 65 to 85% by weight, preferably from 70 to 80% by weight, based on C1.1, of at least one monomer from the group consisting of vinylaromatics (e.g.styrene, α -methylstyrene), ring-substituted vinylaromatics (e.g.p-methylstyrene, p-chlorostyrene) and (C1-C8) -alkyl methacrylates (e.g.methyl methacrylate, ethyl methacrylate)

C1.1.2) from 15 to 35% by weight, preferably from 20 to 30% by weight, based on C1.1, of at least one monomer from the group consisting of vinyl cyanides (e.g.unsaturated nitriles, such as acrylonitrile and methacrylonitrile), (C1-C8) alkyl (meth) acrylates (e.g.methyl methacrylate, N-butyl acrylate, t-butyl acrylate) and derivatives (e.g.anhydrides and imides) of unsaturated carboxylic acids (e.g.maleic anhydride and N-phenylmaleimide)

C1.2) from 95 to 5% by weight, preferably from 90 to 30% by weight, particularly preferably from 80 to 40% by weight, based on component C1, of at least one elastomeric graft base.

The grafting base preferably has a glass transition temperature of <0 ℃, more preferably < -20 ℃, particularly preferably < -60 ℃.

Unless otherwise specified in the present invention, the glass transition temperature is determined by means of dynamic differential calorimetry (DSC) according to standard DIN EN 61006 at a heating rate of 10K/min, with Tg being defined as the midpoint temperature (tangent method) and nitrogen as protective gas.

The graft particles in component C1 preferably have a median particle size (D50 value) of from 0.1 to 0.8 μm, preferably from 0.15 to 0.6. mu.m, particularly preferably from 0.2 to 0.5. mu.m.

The median particle size D50 is the diameter above which 50% by weight of the particles lie and below which 50% by weight lie.

The particle size distribution of the grafted particles and the values derived therefrom were determined by ultracentrifugation measurements (W. Scholtan, H.Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).

In a preferred embodiment, the emulsion graft polymers according to component C1 contain less than 15% by weight, particularly preferably less than 10% by weight, very particularly preferably less than 5% by weight, based on the gel content of the polymer, of graft particles having a particle diameter of more than 800 nm.

Preferably, monomer C1.1.1 is selected from at least one of the monomers styrene, α -methyl styrene, and methyl methacrylate, and preferably monomer C1.1.2 is selected from at least one of the monomers acrylonitrile, maleic anhydride, and methyl methacrylate.

Particularly preferred monomers are C1.1.1 styrene and C1.1.2 acrylonitrile.

Suitable graft bases C1.2 for the graft polymers C1 are, for example, diene rubbers, diene-vinyl block copolymer rubbers, ep (d) M rubbers, i.e. those based on ethylene/propylene and optionally diene, acrylate rubbers, polyurethane rubbers, silicone rubbers with = silicone rubbers, chloroprene rubbers and ethylene/vinyl acetate rubbers and mixtures of these rubbers or silicone-acrylate composite rubbers in which the silicone and acrylate components are chemically linked to one another (for example by grafting).

Preferred graft bases C1.2 are diene rubbers (for example based on butadiene or isoprene), diene-vinyl block copolymer rubbers (for example based on butadiene and styrene blocks), copolymers of diene rubbers with other copolymerizable monomers (for example according to C1.1.1 and C1.1.2), and mixtures of the abovementioned rubber types. Particularly preferred are pure polybutadiene rubber and styrene-butadiene block copolymer rubber.

The gel content of the graft polymer is at least 15% by weight, preferably at least 60% by weight, particularly preferably at least 75% by weight (measured in acetone).

Unless otherwise specified in the present invention, the gel content of the graft polymer was determined as the insoluble content in acetone solvent at 25 ℃ (M. Hoffmann, H. Kr ö mer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).

Graft polymer C1 was prepared by free-radical polymerization.

Graft polymer C1 generally comprises, as a result of manufacture, C1.1.1 and C1.1.2 free copolymers which are soluble in a suitable solvent (e.g., acetone), i.e., copolymers which are not chemically bonded to the rubber graft base.

Component C2

Component C2 is a graft polymer prepared in a bulk, solution or suspension polymerization process by grafting C2.1) onto C2.2)

C2.1) from 5 to 95% by weight, preferably from 80 to 93% by weight, particularly preferably from 85 to 92% by weight, very particularly preferably from 87 to 93% by weight, based on the component C2, of a mixture of C2.1.1) and C2.1.2)

C2.1.1) from 65 to 85% by weight, preferably from 70 to 80% by weight, based on the mixture C.2.1, of at least one monomer from the group consisting of vinylaromatics (e.g.styrene, α -methylstyrene), ring-substituted vinylaromatics (e.g.p-methylstyrene, p-chlorostyrene) and (C1-C8) -alkyl methacrylates (e.g.methyl methacrylate, ethyl methacrylate)

C2.1.2) 15 to 35% by weight, preferably 20 to 30% by weight, based on the mixture C2.1, of at least one monomer from the group consisting of vinyl cyanides (e.g. unsaturated nitriles, such as acrylonitrile and methacrylonitrile), (meth) acrylic acid (C1-C8) alkyl esters (e.g. methyl methacrylate, N-butyl acrylate, t-butyl acrylate) and derivatives (e.g. anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-phenylmaleimide)

C2.2) from 95 to 5% by weight, preferably from 20 to 7% by weight, particularly preferably from 15 to 8% by weight, very particularly preferably from 13 to 7% by weight, based on component C2, of at least one graft base.

The graft base preferably has a glass transition temperature of <0 ℃, preferably < -20 ℃, particularly preferably < -60 ℃.

The graft particles in component C2 preferably have a median particle size (D50 value) of from 0.1 to 2 μm, preferably from 0.2 to 1 μm, particularly preferably from 0.3 to 0.7. mu.m.

The particle size distribution of the grafted particles and the values derived therefrom were determined by ultracentrifugation measurements (W. Scholtan, H.Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).

In a preferred embodiment, the graft polymers according to component C2 contain less than 40% by weight, particularly preferably less than 30% by weight, in particular less than 20% by weight, based on the gel content of the graft polymer, of graft particles having a particle diameter of more than 800 nm.

Preferably, monomer C2.1.1 is selected from at least one of the monomers styrene, α -methyl styrene, and methyl methacrylate, and preferably monomer C2.1.2 is selected from at least one of the monomers acrylonitrile, maleic anhydride, and methyl methacrylate.

Particularly preferred monomers are C2.1.1 styrene and C2.1.2 acrylonitrile.

Preferred graft bases C2.2 are diene rubbers (for example based on butadiene or isoprene), diene-vinyl block copolymer rubbers (for example based on butadiene and styrene blocks), copolymers of diene rubbers with other copolymerizable monomers (for example according to C2.1.1 and C2.1.2), and mixtures of the abovementioned rubber types. Particularly preferred graft bases C2.2 are polybutadiene rubber, styrene-butadiene block copolymer rubber and mixtures of styrene-butadiene block copolymer rubber and polybutadiene rubber.

The gel content of the graft polymer C2 is preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight, very particularly preferably from 17 to 23% by weight (measured in acetone).

Particularly preferred polymers C2 are ABS polymers, for example prepared by free-radical polymerization, which in a preferred embodiment contain up to 10% by weight, particularly preferably up to 5% by weight, particularly preferably from 2% by weight to 5% by weight, of n-butyl acrylate, based in each case on the graft polymer C2.

Graft polymer C2 generally contains, as a result of manufacture, C2.1.1 and C2.1.2 free copolymers characterized as being soluble in a suitable solvent (e.g., acetone), i.e., copolymers that are not chemically bonded to a rubber substrate.

Component C2 preferably contains C2.1.1 and C2.1.2 free copolymers having a weight-average molecular weight (Mw) of preferably 50000 to 200000 g/mol, particularly preferably 70000 to 160000 g/mol, particularly preferably 80000 to 120000 g/mol, determined by gel permeation chromatography using polystyrene standards.

Component C3

The composition may contain as a further component C3 a (co) polymer of at least one monomer selected from the group consisting of vinyl aromatic hydrocarbons, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C1-C8) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.

Particularly suitable as component C3 are (co) polymers of C3.1 and C3.2

C3.1 from 50 to 99% by weight, preferably from 65 to 85% by weight, particularly preferably from 70 to 80% by weight, based on the (co) polymer C3, of at least one monomer from the group consisting of vinyl aromatics (e.g.styrene, α -methylstyrene), ring-substituted vinyl aromatics (e.g.p-methylstyrene, p-chlorostyrene) and (C1-C8) -alkyl methacrylates (e.g.methyl methacrylate, n-butyl acrylate, tert-butyl acrylate),

c3.2 from 1% to 50% by weight, preferably from 15% to 35% by weight, particularly preferably from 20% to 30% by weight, based on the (co) polymer C3, of at least one monomer from the group consisting of vinyl cyanides (e.g.unsaturated nitriles, such as acrylonitrile and methacrylonitrile), (meth) acrylic acid (C1-C8) alkyl esters (e.g.methyl methacrylate, N-butyl acrylate, tert-butyl acrylate), unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids (e.g.maleic anhydride and N-phenylmaleimide).

These (co) polymers C3 are resinous, thermoplastic and rubber-free. Copolymers of C3.1 styrene and C3.2 acrylonitrile are particularly preferred.

(Co) polymers C3 of this type are known and can be produced by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers C3 have a weight-average molecular weight (Mw) determined by gel permeation chromatography using polystyrene standards of preferably 50000 to 200000 g/mol, particularly preferably 70000 to 150000 g/mol, particularly preferably 80000 to 120000 g/mol.

Component D

The compositions may contain, as component D, one or more further additives which are different from components A, B, C and E and are preferably selected from the group consisting of flame retardants (for example organic phosphorus-or halogen compounds, in particular oligophosphates based on bisphenol A), anti-dripping agents (for example compounds from the class of fluorinated polyolefins, silicones and aramid fibers), flame-retardant synergists (for example nanoscale metal oxides), smoke suppressants (for example zinc borate), lubricating-and mould-release agents (for example pentaerythritol tetrastearate), nucleating agents, antistatics, electrically conductive additives, stabilizers (for example hydrolysis-, thermal-ageing-and UV-stabilizers, and transesterification inhibitors), flow promoters, compatibilizers, further impact modifiers (with or without core-shell structure), further polymer components (for example functional blend partners), Fillers and reinforcing agents (e.g. carbon fibres, talc, mica, kaolin, CaCO)₃) And dyes and pigments (e.g., titanium dioxide or iron oxide).

In a preferred embodiment, the composition contains at least one polymer additive selected from the group consisting of lubricating and mold release agents, stabilizers, flow promoters, compatibilizers, other impact modifiers, other polymer components, dyes and pigments.

In a particularly preferred embodiment, the composition contains at least one polymer additive selected from the group consisting of lubricating and mold release agents, stabilizers, flow promoters, compatibilizers, further impact modifiers different from component C, further polymer components, dyes and pigments and is free of further polymer additives.

In a preferred embodiment, the composition contains pentaerythritol tetrastearate as mold release agent.

In a preferred embodiment, the composition contains as stabilizer at least one member selected from the group consisting of sterically hindered phenols, organophosphites and sulfur-based co-stabilizers.

In a particularly preferred embodiment, the composition contains at least one member selected from the group consisting of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite as a stabilizer.

In a particularly preferred embodiment, the composition contains a combination of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite as stabilizer.

Further preferred compositions contain pentaerythritol tetrastearate as mold release agent, a combination of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite as stabilizer, optionally at least one pigment or colorant and no other polymer additives.

Component E

The polyesters which are considered as component E according to the invention are aliphatic or aromatic polyesters, preferably aromatic polyesters, in a particularly preferred embodiment polyalkylene terephthalates. In a particularly preferred embodiment, this is the reaction product of an aromatic dicarboxylic acid or a reactive derivative thereof, such as a dimethyl ester or anhydride, with an aliphatic, cycloaliphatic or araliphatic diol, and also mixtures of these reaction products.

Particularly preferred polyalkylene terephthalates contain at least 80 wt.%, preferably at least 90 wt.%, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 80 wt.%, preferably at least 90 wt.%, based on the diol component, of ethylene glycol and/or butane-1, 4-diol radicals.

Preferred polyalkylene terephthalates may contain, in addition to terephthalic acid radicals, up to 20 mol%, preferably up to 10 mol%, of radicals of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as, for example, radicals of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4' -diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.

Preferred polyalkylene terephthalates may contain, in addition to ethylene glycol and/or butane-1, 4-diol radicals, up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, for example radicals of propane-1, 3-diol, 2-ethylpropane-1, 3-diol, neopentyl glycol, pentane-1, 5-diol, hexane-1, 6-diol, cyclohexane-1, 4-dimethanol, 3-ethylpentane-2, 4-diol, 2-methylpentane-2, 4-diol, 2, 4-trimethylpentane-1, 3-diol, 2-ethylhexane-1, 3-diol, 2-diethylpropane-1, 3-diol, hexane-2, 5-diol, 1, 4-bis (β -hydroxyethoxy) benzene, 2-bis (4-hydroxycyclohexyl) propane, 2, 4-dihydroxy-1, 1,3, 3-tetramethylbutane, 2, 4-bis (357684-hydroxyethoxyphenyl) propane, 2-bis (2407674, 2407776, 2715932).

The polyalkylene terephthalates may be branched by incorporating relatively small amounts of trihydric or tetrahydric alcohols or tribasic or tetrabasic carboxylic acids, for example according to DE-A1900270 and U.S. Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.

Particularly preferred are polyalkylene terephthalates that have been produced solely from terephthalic acid and its reactive derivatives (e.g.its dialkyl esters) and ethylene glycol and/or butane-1, 4-diol, and mixtures of these polyalkylene terephthalates.

The mixture of polyalkylene terephthalates contains 1 to 50 wt.%, preferably 1 to 30 wt.%, of polyethylene terephthalate and 50 to 99 wt.%, preferably 70 to 99 wt.%, of polybutylene terephthalate.

The polyalkylene terephthalates preferably used preferably have viscosity numbers of 0.4 to 1.5 dl/g, preferably 0.5 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1: 1 parts by weight) at 25 ℃ in a concentration of 0.05 g/ml in an Ubbelohde viscometer according to ISO 307.

The polyalkylene terephthalates may be produced by known methods (see, for example, Kunststoff-Handbuch, volume VIII, p.695 et seq., Carl-Hanser-Verlag, M ü nchen 1973).

The compositions (molding compounds) prepared by the process according to the invention can be used for the production of moldings of all kinds. These can be manufactured by, for example, injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from prefabricated sheets or films.

Examples of such moldings are films, profiles, housing parts of various types, for example for household appliances such as juice extractors, coffee machines, mixers; for office equipment such as displays, flat screens, notebook computers, printers, copiers; sheets, tubes, electrical installation conduits, windows, doors and other profiles for the building industry (interior finishing and outdoor use), as well as electrical and electronic components, such as switches, plugs and sockets, and components for commercial vehicles, in particular for the automotive industry. The compositions according to the invention are also suitable for the production of the following mouldings or mouldings: interior trim parts for rail vehicles, ships, airplanes, buses and other motor vehicles, body parts for motor vehicles, housings for electrical equipment containing miniature transformers, housings for information processing and transmission equipment, housings and panels for medical equipment, massage equipment and housings therefor, children's toy vehicles, flat wall elements, housings for safety devices, thermally insulated transport containers, moldings for sanitary and bathroom equipment, protective grilles for ventilation openings and housings for gardening equipment.

The compositions according to the invention are particularly suitable for coloring themselves by direct addition of colorant masterbatches during thermoforming (Selbstein f ä rbung), owing to their stable light inherent color during processing.

The compositions according to the invention are also particularly suitable for producing moldings or mouldings having a class A surface requirement and a high gloss finish, which may optionally be subjected partially or completely to further surface treatment steps, for example by painting, film post-injection (Hinterspritzng), metallization by vacuum evaporation or electroplating.

In the context of the present invention, "high gloss" and "high gloss finish" are understood to mean a gloss measured by reflection at a measurement angle of 60 ° according to DIN 67530 of at least 95, preferably at least 97, particularly preferably at least 99.

The invention therefore also relates to moldings or moldings of all types, preferably those having a completely or partially high-gloss finish, made from the compositions according to the invention, which have optionally been subjected, partially or completely, to further surface treatment steps (for example by painting, film post-injection molding, metallization by vacuum evaporation or electroplating).

Examples

The components used were:

component A

Linear polycarbonate based on bisphenol A with a weight-average molecular weight Mw of 28000 g/mol (determined by Gel Permeation Chromatography (GPC) using polycarbonate standards in methylene chloride solvent)

Component B1

Trilon^®BS Ethylene Diamine Tetraacetic Acid (EDTA), BASF (Ludwigshafen, Germany)

Component B2

Phenylphosphonic acid (98%), Sigma-Aldrich Chemie GmbH

Component B3

Citric acid (not less than 99.5%), Merck KGaA

Component B4

Oxalic acid (. gtoreq.99.0%), Sigma-Aldrich Chemie GmbH

Component B5

Terephthalic acid (98%), Sigma-Aldrich Chemie GmbH

Component B6

Phosphorous acid (99%) (Sigma-Aldrich Chemie GmbH).

Component B7

Fabutit^®313: Ca(H₂PO₄)₂Chemische Fabrik Budenheim KG (Budenheim, Germany)

Component B8

P-toluenesulfonic acid (98%), Alfa Aesar GmbH & Co KG

Component C

ABS blends having a ratio of acrylonitrile to butadiene to styrene of 20% by weight to 18% by weight to 62% by weight, based on the blend, containing ABS polymers which are produced in emulsion polymerization, precipitated with magnesium sulfate, worked up in an alkaline environment and contain an alkaline component and magnesium sulfate, ABS polymers produced in bulk polymerization and SAN polymers

Component D1

Pentaerythritol tetrastearate as lubricant/mold release agent

Component D2

Heat stabilizer, Irganox^®B900（80% Irgafos^®168 (tris (2, 4-di-tert-butylphenyl) phosphite) and 20% Irganox^®1076 (mixture of 2, 6-di-tert-butyl-4- (octadecyloxycarbonylethyl) phenol), BASF (Ludwigshafen, Germany)

Component D3

Heat stabilizer, Irganox^®1076 (2, 6-di-tert-butyl-4- (octadecyloxycarbonylethyl) phenol), BASF (Ludwigshafen, Germany).

Method for producing a composition (moulding compound) from the components used

In a first process step (i), components A, B, C and D are mixed at room temperature and the mixture is introduced at a throughput of 20 kg/h from Coperion, Werner&Feed zone of a ZSK25 twin-screw extruder from Pfleiderer (Stuttgart, Germany). In the melt-and kneading zones of the extruder at 220 and 500 min^-1Is brought to a temperature of 260 ℃ and 290 ℃ and is thereby melted, and is brought toKneading at this temperature and thereby dispersing the components in each other. The mixture thus compounded is degassed in a subsequent degassing zone of the extruder by applying a negative pressure of 100 mbar (absolute) to the melt. In a second process step (ii), the degassed melt is discharged from the extruder at the above-mentioned temperatures of 260 ℃ and 290 ℃ via a nozzle and the resulting melt strand is cooled by passing it through a water bath which is tempered to about 30 ℃.

In a third method step (iii), the solidified melt strand is granulated by means of strand granulation.

Fabrication and testing of test specimens

Pellets from each compound were processed in an injection molding machine (from Arburg corporation) at melt temperatures of 260 ℃ and 300 ℃ and a mold temperature of 80 ℃ to provide samples having dimensions of 60 mm x 40 mm x2 mm (for determining yellowness and gloss), and at melt temperature of 260 ℃ and a mold temperature of 80 ℃ to provide samples having dimensions of 150 mm x 105 mmx 3.2 mm (for determining blistering (Blister) behaviour after hot and humid storage). Both sample types were manufactured using highly polished injection molds.

MVR serves as a measure of the possible reduction in the molecular weight of the polycarbonate during the thermal stress of compounding and is determined according to ISO1133 on pellets produced by compounding after drying at 110 ℃ for 4 hours in a circulating air dryer after a holding time of 5 minutes with a 5 kg punch load at a melt temperature of 300 ℃.

iMVR was determined under the same conditions as MVR but with an extended hold time of 15 minutes.

Relative improvement in iMVR relative to MVR

ΔMVR(300℃/5kg, 5min→15min) = 100% · (iMVR - MVR) / MVRServes as a measure of the expected reduction in the molecular weight of the polycarbonate at elevated processing temperatures in injection molding and thus as a measure of the processing stability of the composition in injection molding.

The natural hue/intrinsic color is measured in reflection according to DIN 6174 on flakes having dimensions of 60 mm X40 mm X2 mm and produced in injection molding at melt temperatures of 260 ℃ and 300 ℃. The yellowness index (yellowness index YI) was calculated according to ASTM E313.

Gloss was measured on sheets having dimensions of 60 mm x 40 mm x2 mm and made in injection moulding at melt temperatures of 260 ℃ and 300 ℃. The measurement was carried out in reflection according to DIN 67530 at a measurement angle of 60 °.

The absolute change in yellowness and gloss at increasing the melt temperature in injection molding from 260 ℃ to 300 ℃ serves as a further important parameter for characterizing the processing stability, which is calculated as follows

Δ yellowness value (260 ℃ → 300 ℃) = yellowness value (300 ℃) -yellowness value (260 ℃)

And

Δ gloss (260 ℃ → 300 ℃) = gloss (300 ℃) -gloss (260 ℃)。

It was evaluated whether the yellowness value measured on the test specimens produced in injection molding at a melt temperature of 260 ℃ is less than 25 and whether the gloss of these test specimens is greater than 95. It was also evaluated whether the absolute changes in yellowness and gloss were respectively less than 10 when the processing temperature in injection molding was increased from 260 ℃ to 300 ℃. This corresponds to the usual requirement for moulding compounds which are stable during processing and are set up for pigmented and high-gloss applications.

The relative change in MVR measured at 260 ℃ with a punch load of 5 kg and a retention time of 5 minutes in accordance with ISO1133 under moist heat conditions of 95 ℃ and 100% relative air humidity for 7 days ("FWL storage") serves as a measure of the hydrolysis resistance of the composition. The relative increase in MVR value, relative to the MVR value before the corresponding storage, is calculated as Δ MVR (hydr), which is defined by the following formula:

。

the tendency to form surface defects with a blistered topology was determined on sheets with a geometry of 150 mm x 105 mm x 3.2 mm and a high gloss surface on both sides. These sheets generally show no blistering whatsoever immediately after injection molding. In these sheets at 40 ℃ and>the product is stored under humid and hot condition with relative air humidity of 95% for three days without usingGross technical aids (microscope, magnifying glass, etc.) visually assess blistering. Here, a total of two sheets having the above-specified dimensions were counted on both sides (i.e., 4 · 15 cm · 10.5 cm = 630 cm)²On the effective surface area of the substrate) of all visually observable blister defects. According to experience, this purely visual assessment without the aid of magnification techniques noted all defects with a diameter higher than about 100-. It is evaluated whether this count observes less than 10 blister defects, which corresponds to a generally acceptable quality.

The examples in Table 1 show that the moulding compositions according to the invention according to example 1/1b, which were produced using EDTA alone and contained it as acidic compound, fully achieve the object of the invention, whereas the compositions according to comparative examples V2 to V8, which were produced using acids according to the prior art, all deviate from the target property profile at least in respect of one of the desired properties.

The compositions made with phenylphosphonic acid (V2) showed unacceptable hydrolytic stability and unacceptable foaming behaviour.

The compositions made with citric acid (V3) exhibited unacceptable gloss stability and unacceptable foaming behaviour.

Compositions made with oxalic acid (V4/V4b) exhibit increased heat-induced polycarbonate molecular weight reduction even during compounding at elevated melt temperatures (i.e., a processing window that fails in compound manufacture) and processing stability in polycarbonate molecular weight reduction in injection molding of such compounds made under more severe thermal conditions.

Compositions made with terephthalic acid, phosphorous acid or monocalcium phosphate (V5-V7) all showed unacceptable foaming behavior.

The compositions (V8) made with p-toluenesulfonic acid showed unacceptable hydrolytic and gloss stabilities and unacceptable foaming behaviour.

Claims (15)

1. Composition of matter comprising

A) At least one polymer selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates, and

B) at least one Bronsted acidic compound selected from the group consisting of compounds of the general formulae (I) and (II)

(R1)_y1-N-[R2-COOH]_x1(I)

[HOOC-R2]_x2(R1)_y2N-(R3)-N(R1)_y3[R2-COOH]_x3(II)

Wherein

R1 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

r2 represents C₁-to C₈Alkylene or C₂-to C₈-an alkylidene group having a structure represented by the formula,

r3 represents- (CH)₂)_n–、–(CH₂)_n[O(CH₂)_n]_m-or- (CH)₂)_n[NR4(CH₂)_n]_m–，

n is an integer number which is the number,

m is an integer which is a whole number,

r4 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

x1 is an integer from 1 to 3,

x2 and x3 are each 1 or 2,

and is

y1 is calculated by the formula y1= 3-x 1,

y2 is calculated by the formula y2= 2-x 2,

and y3 is calculated by the formula y3= 2-x 3,

wherein in the compounds having a plurality of radicals R1 and/or R2, these radicals may, independently of one another, represent different or identical radicals having the abovementioned definition.

2. A composition as claimed in claim 1, characterised in that component B is selected from Ethylene Diamine Tetraacetic Acid (EDTA), nitriloacetic acid, ethylene glycol bis (aminoethyl ether) -N, N' -tetraacetic acid (EGTA) and diethylenetriaminepentaacetic acid (DTPA).

3. Composition as claimed in any of the preceding claims, characterized in that ethylenediaminetetraacetic acid (EDTA) is used as component B.

4. A composition as claimed in any one of claims 1 to 2, characterized in that component B is contained in the composition in a content ranging from 0.00001% to 0.5% by weight.

5. A composition as claimed in any one of claims 1 to 2, characterized in that it further comprises as component C one or more rubber-containing graft polymers and/or rubber-free vinyl homo-or copolymers.

6. A composition as claimed in claim 5, characterized in that component C comprises at least one rubber-containing graft polymer prepared by emulsion polymerization.

7. A composition as claimed in any one of claims 1 to 2, characterized by comprising at least one alkali metal-, alkaline earth metal-, aluminium-or transition metal salt of a strong mineral acid.

8. The composition of claim 7, wherein the salt is magnesium sulfate.

9. A process for preparing a thermoplastic polycarbonate composition comprising steps (i), (ii) and optionally (iii), wherein

In the first step (i)

Heating A) and B) and optionally further components by supplying heat and/or mechanical energy, thereby melting at least component A, the components being dispersed in one another, and subsequently degassing the resulting composition in the form of a melt, optionally by applying an underpressure,

A) at least one polymer selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates,

B) at least one Bronsted acidic compound selected from the group consisting of compounds of the general formulae (I) and (II)

(R1)_y1-N-[R2-COOH]_x1(I)

[HOOC-R2]_x2(R1)_y2N-(R3)-N(R1)_y3[R2-COOH]_x3(II)

Wherein

R1 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

r2 represents C₁-to C₈Alkylene or C₂-to C₈-an alkylidene group having a structure represented by the formula,

r3 represents- (CH)₂)_n–、–(CH₂)_n[O(CH₂)_n]_m-or- (CH)₂)_n[NR4(CH₂)_n]_m–，

n is an integer number which is the number,

m is an integer which is a whole number,

r4 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

x1 is an integer from 1 to 3,

x2 and x3 are each 1 or 2,

and is

y1 is calculated by the formula y1= 3-x 1,

y2 is calculated by the formula y2= 2-x 2,

and y3 is calculated by the formula y3= 2-x 3,

wherein in the compounds having a plurality of radicals R1 and/or R2, these radicals may, independently of one another, represent different or identical radicals having the abovementioned definition,

wherein at least one of the components used in step (i) is basic or contains a component that is basic,

and in a further step (ii)

Re-solidifying the resulting composition by cooling

And granulated in a further step (iii),

wherein these further steps (ii) and (iii) may be performed in any order.

10. A process as claimed in claim 9, characterized in that component B is selected from ethylenediaminetetraacetic acid (EDTA), nitriloacetic acid, ethylene glycol bis (aminoethyl ether) -N, N' -tetraacetic acid (EGTA) and diethylenetriaminepentaacetic acid (DTPA).

11. A process as claimed in claim 9 or 10, characterized in that at least one rubber-containing graft polymer prepared by emulsion polymerization and optionally at least one further component selected from rubber-containing graft polymers prepared by mass-, solution-or suspension polymerization and rubber-free vinyl homopolymers or copolymers are also used as component C, and component C contains at least one alkali metal, alkaline earth metal, aluminum or transition metal salt of a strong mineral acid.

12. Use of acids according to the general formula (I) or (II) for stabilizing polycarbonate compositions

(R1)_y1-N-[R2-COOH]_x1(I)

[HOOC-R2]_x2(R1)_y2N-(R3)-N(R1)_y3[R2-COOH]_x3(II)

Wherein

R1 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

r2 represents C₁-to C₈Alkylene or C₂-to C₈-an alkylidene group having a structure represented by the formula,

r3 represents- (CH)₂)_n–、–(CH₂)_n[O(CH₂)_n]_m-or- (CH)₂)_n[NR4(CH₂)_n]_m–，

n is an integer number which is the number,

m is an integer which is a whole number,

r4 represents alkyl, aryl or cycloalkyl optionally functionalized or substituted by heteroatoms,

x1 is an integer from 1 to 3,

x2 and x3 are each 1 or 2,

and is

y1 is calculated by the formula y1= 3-x 1,

y2 is calculated by the formula y2= 2-x 2,

and y3 is calculated by the formula y3= 2-x 3,

and wherein in the compounds having a plurality of radicals R1 and/or R2, these radicals may, independently of one another, represent different or identical radicals having the abovementioned definition.

13. A composition made by any of the methods of claims 9-11.

14. Use of a composition as claimed in any of claims 1 to 8 and 13 for the manufacture of a moulded article.

15. A molded article comprising the composition as claimed in any one of claims 1 to 8 and 13.